GB2029457A - Saltcoated magnesium granules - Google Patents

Description

1 GB2029457A 1

SPECIFICATION

Salt-coated magnesium granules The present invention resides in a process for recovering rotund, salt- coated Mg particles, or Mg alloy particles, from entrapment in a contiguous, friable matrix of sludge or slag material.

More specifically, the present invention resides in a process for recovering rotund, salt-coated particles without flattening, rupturing, or pulverizing said particles. Moreover, such rotund Mg particles are recovered in a manner such that the Mg particles retain only a thin protective coating of the sludge material in which they are entrapped. The coated Mg particles are recovered with a relatively consistent Mg content and a relatively consistent particle size range and rotundity for use as an inoculant through a lance into a molten ferrous metal.

The present invention also resides in a process for the preparation of a contiguous, friable, matrix of salt material containing dispersed therein discrete, rotund particles of Mg or Mg alloy.

It is well known in the iron and steel industry that Mg metal is a useful inoculant for addition 15 to molten ferrous metals; the Mg is known to be an effective desulfurizing agent for steel and is an effective nodularizing agent for preparing ductile iron.

It is also well known that Mg, as small particles, may be added to the molten ferrous metal by being carried through a lance by a stream of gas or in a carrier.

Mg metal, especially when in finely-divided form, is easily oxidized and is sometimes pyrophoric. In contact with water, it gives off H2 which, in ample quantities, presents an explosion or fire hazard. Various methods for reducing the pyrophoric and explosive hazards have been developed over the years and these developments have met with sufficient success to cause the iron and steel industry to remain interested in obtaining an economical, small particle Mg inoculant material which is relatively safe to store and use and which performs in a consistent, effective manner.

In the electrolytic production of magnesium by the electrolysis of molten MgC121 it has been known for many years that the presence of boron values of the MgC12 is detrimental to the complete coalescence of molten Mg formed during the electrolysis. It is known that seawater contains small amounts of boron and when seawater is treated with an alkaline material to precipitate Mg(OH)2, a small amount of boron values may be also precipitated. Then when the Mg(OH)2 is chlorinated to obtain MgC12 for use as a feed material (also called "cell bath") to an electrolytic Mg cell, a detrimental amount of the boron values may accompany the MgC12 unless steps are taken to remove, or at least substantially reduce, the amount of boron values. Thus, in the field of magnesium production, the attention given to boron values has been toward 35 removing the boron values from the system. Even with such attempts made over the years to obtain substantially complete coalescence of molten Mg, formed in the fused salt electrolysis of MgC121 so as to obtain a separable molten Mg phase, there is always some Mg which remains dispersed as droplets in the molten salt and in the cell sludge which is removed from the cell.

When the cell sludge or the cell bath material is removed from the cell and freezes to a relatively 40 hard (though friable) mass the small beads of Mg trapped therein in small quantities may be wasted unless there is provided an economical means for salvaging or utilizing the materials.

Ordinarily the amount of Mg trapped in these frozen salt mixtures is only a small percentage of less than 20%, usually less than 15%, by weight.

It is also known that in Mg alloying processes, e.g., the alloying of Mg and Al, the alloying is 45 usually performed under a protective blanket of a molten salt flux. Some of the Mg alloy is retained in the flux material and removed from the alloying process as a "slag". These alloying process slags, somewhat similar to the frozen cell baths or cell sludges, contain small percentages of Mg alloy as discrete particles trapped therein.

In the past, efforts have been made to pulverize these matrices of sludges and slags into 50 particle sizes suitable for commercial use as inoculants for molten ferrous melts, but because of batch-to-batch variations and the high salt content, the efforts had only limited success.

Also, there have been commercial efforts over the years to pulverize these sludges and slags to free the Mg particles from entrapment in the friable salt matrix and screen the particles from the salt or wash the water-soluble salts from the Mg particles. The Mg particles thus freed have 55 been remelted for recovery and cast into ingots. The cost of obtaining such secondary Mg or Mg alloy in ingot form from sludges and slags requires comparison with the cost of primary Mg or Mg alloy ingots obtained from the principal sources, i.e., the electrolytic cell output or the alloying process output. Usually, if the market price of primary Mg or Mg alloy ingot is down because of decreased market demand, the recovery of secondary Mg or Mg alloy ingot from 60 sludges or slags is not economical so that there is little or no incentive to perform the secondary recovery.

However, it has now been found that there are economical incentives for developing processes which will recover Mg or Mg alloy pellets from entrapment in sludges and slags (even though the pellets still contain a surface coating of the sludge or slag material) for use other 65 2 GB 2 029 457A.2 than as casting into ingots. In fact, such pellets are useful as an inoculant material for molten ferrous melts and the protective salt coating is found to be beneficial, rather than detrimental.

The separation of solid Mg metal spheroids from entrapment in a solid contiguous matrix of a friable salt or mixture of salts presents particular problems to an investigator who may desire to recover the Mg in its spheroidal form and also retain on each spheroid a thin protective coating of the matrix material. Whereas it has been known for many years that such a Mg-containing matrix is removed as cell sludge from the electrolysis of molten MgCl, and as a slag material from Mg or Mg-alloy casting operations, attempts to recover the Mg or Mg alloy particles by grinding or intensive ball-milling have generally resulted in smashing, breaking, or flattening a large portion of the Mg particles. Such deformed particles may be acceptable if the principal 10 purpose of recovering the metal is that of re-melting it for coalescence or for re-casting as ingots.

In the present invention, however, what is of special interest is the recovery, from the solid matrix, of Mg spheroids which each have a thin protective coating of the matrix remaining - thereon. Such spheroidal Mg particles are of particular interest for use in inoculating molten 15 ferrous metals, e.g., the desulfurization of steel. The thin protective coating of matrix on the Mg spheroids helps avoid the hydrolysis of Mg by moisture or the oxidation of Mg by air. Mg particles which are substantially flattened or elongated or which do not have a high degree of rotundity are not as readily useful in operations where the particles are injected through a lance benbath the surface of molten iron or steel. Ideally, the operators of such lances would prefer 20 that the Mg particles be of consistent size, consistent Mg content, and consistent rotundity in order to avoid unwelcome variances during the inoculation process.

The use of various grinding or pulverizing machines for reducing the particle size of various solid materials, such as rocks, ores and minerals, is well known. The use of screens or nests of screens to separate particles into various ranges of sizes is also well known. Very often the 25 screens are vibrated to effect better, faster separations.

The separation of rotund beads from irregular shaped particles on a slanted surface is taught, e.g., in French Patent 730,215; U.S. 1,976,974; U.S. 2,778,498; U.S. 2, 658,616; and U.S.

3,464, 550. A U.S. Department of Interior, Bureau of Mines publication R. I. 4286 dated May, 1948 on "New Dry Concentrating Equipment" contains information on a vibrating-deck mineral 30 shape separator; the separator disclosed is a vibrated tilted table where the trajectory of particles across the surface is dependent on the shape of the particles. There are various sludges and slags from mining and metallurgical operations which are known to contain inclusions of metal droplets, such as copper, nickel, tin, and others.

U.S. 3,037,711 teaches the use of beater mills or hammer mills for pulverizing dross from 35 metal particles, then separating the fines from the particles by suction.

General information about pulverizers, screens, and tabling may be found in, e.g., "Chemical Engineers Handbook" by Robt. H. Perry, Editor, published by McGraw-Hill.

Q.S. 3,881,913 and U.S. 3,969,104 disclose the preparation of salt-coated Mg granules by an atornization technique and also disclose that such granules are useful for injection into 40 molten iron through a lance.

Patents which teach the formation of small particles of Mg or Mg alloy on a spinning disc are, e.g., U.S. 2,699,576; U.S. 3,520,718; and U.S. 3,881,913.

The salt which may be employed in the present invention as the "matrix" material may be a single compound, such as a halide of Na, K, Li, Mg, Ca, Ba, Mn or Sr or may be a mixture of 45 two or more of these salts. It is possible, and in some cases desirable, to employ mixtures of salts wherein the halide of one or more of the salts is a different halide than of the other salts.

For instance, mixtures Of MgCl2, NaCl, LiCl (or KCI), and CaF2 may be employed in various proportions. As used herein, the term "salt" comprises ingredients which are predominantly halide salts, but may also contain up to 25% of oxides or other salts.

Various patents have described the molten salt mixtures, containing MgCl2, which may be employed in electrolytic cells for the electrolytic production of Mg metal, e.g., U.S. 2,888,389; U.S. 2,950,236; and U.S. 3,565,917. It is disclosed that the composition of the salt mixture may be varied in order to adjust the density to be greater than, or less than, molten Mg metal.

Slidges formed in such electrolytic Mg processes are known to contain Mg metal particles entrapped in a matrix of salt, and, usually there are some Mg oxide values also present, due to contact with air or moisture. The use of fluorides in the salt mixtures as coalescing agents for the Mg metal is disclosed. Mixtures of salts are taught in U.S. 3,881,913 which are recognizable as mixtures such as are known to be employed in electrolytic Mg production as "cell bath" electrolyte compositions. Such cell bath compositions are also known to be present 60 in Mg cell sludge and when the cell sludge is ground up to free the small beads of Mg metal trapped therein, some of the salt mixture is found to be present on the Mg beads as a thin coating.

At the 6th SDCE International Die Casting Congress, organized by The Society of Die Casting Engineers, Inc. at Cleveland, Ohio on November 16-19, 1970, a paper was presented (Paper 65 i L 3 GB 2 029 457A 3 4 No. 10 1) on "Factors Controlling Melt Loss in Magnesium Die Casting", authored by J. N. Reding and S. C. Erickson. The paper discloses the entrapment of Mg particles and Mg alloy particles in sludges and slags, and discloses studies about coalescing agents and dispersion agents (emulsifiers) for the Mg particles. It also discloses the grinding, in a ball mill, of a Mg5 containing sludge to recover the Mg particles from entrapment therein.

Therefore, sludge material from Mg-producing processes, or from Mgcasting operations are known to contain Mg metal entrapped therein. In the Mg-producing processes, e.g., the electrolyzing of molten MgCI, in the presence of other molten salts to produce Cl, and molten Mg, the sludge material is composed of metal salts, oxides, impurities, and contaminants and contains a relatively small amount of Mg particles of various sizes dispersed therein.

During Mg casting, or Mg-alloy casting, the melt flux is usually provided on the surface of the molten metal in the melting vessel to prevent or retard contact of the metal with air or moisture and to prevent Mg fires. Such fluxes are usually mixtures of molten salts such as disclosed in U.S. 2,327,153 which also discloses that small Mg beads become trapped in the frozen sludge or slag as discrete fine globules having a diameter as small as 0.01 inch. The patent also 15 discloses re-melting and stirring the sludge or slag in order to get the small Mg beads to coalesce into large beads of about 0.5 inch or of even larger diameter, then partly cooling and separating the frozen beads from the still-molten salts by filtration.

Thus, the metal salt compositions of Mg cell sludges, Mg-casting slags, and Mg alloy-casting slags are a matter of record and are known to comprise various mixtures and ratios of alkaline 20 metal salts, alkaline earth metal salts, some oxides and, generally, some impurities and contaminants.

In the present invention a boron-containing dispersing agent, with or without the simultane ous addition of a very fine carbon material, is added to a molten mixture of salt and Mg or Mg alloy. The molten mixture is stirred to effect good dispersion of the dispersing agent and the 25 molten metal. The molten mixture is then cooled to a solid state and is broken up and pulverized in a hammer mill to free the metal particles from the salt matrix, leaving only a thin, protective layer of the salt matrix adhering to the surface of the metal particles. The pulverized material is then screened in a very dry atmosphere to substantially separate the rotund metal particles from the pulverized, loose matrix material.

More particularly, the present invention residues in a process which comprises adding a boron-containing dispersing agent to a molten mixture of salt and Mg or Mg alloy, stirring the mixture to obtain thorough mixing of the boron-containing dispersing agent and the molten Mg or Mg alloy in the molten salt, and cooling the mixture, thereby obtaining a frozen, friable, salt matrix having dispersed therein solid rotund particles of Mg or Mg alloy.

The salt-coated Mg particles of interest in the present invention may be called "powders", "beads", "p6liets", 11 granules", or other such term. The particles of greatest interest have a high degree of rotundity, being of a spherical and/or oval shape, and have a particle size in the range of from 8 to 100 mesh (U.S. Standard Sieve size). For the common practice of inoculating ferrous melts through a lance, the preferred particle size is generally within the range 40 of from 10 to 65 mesh, though any particle size which will pass through an 8 mesh screen is operable and is readily adaptable for such use.

As used herein, the expression "high degree of rotundity" is applied to particles, beads, pellets, or granules which-are spherical, or at least nearly spherical, but also includes oval shapes which roll easily on a slightly inclined surface. In contradistinction, particles which are 45 substantially broken, smashed, flattened or irregular and which do not roll easily on a slightly inclined surface are not considered as having a high degree of rotundity. As used herein, rotund" particles refer to metal particles having a "high degree of rotundity".

A "hammer mill", as used herein, implies an apparatus which employs a plurality of swinging or revolving hammer blades or projections which stroke the material fed in, thereby pulverizing 50 the friable material. For purposes of conciseness, the term "hammer mill" is used herein to include all mills which employ the same general type of impact on the particles as does the hammer mill.

"Mg-containing sludges or slags", sometimes referred to herein as "sludge", includes sludge or slag material from a Mg-producing process, or from a Mg-casting or Mg alloy casting operation, which contains particles of Mg (or Mg alloy) entrapped therein. The material which entraps the Mg particles is a friable, contiguous matrix of a frozen salt mixture which may also, and often does, contain some oxides, contaminants, and impurities. As used herein, the expression -Mg- or "magnesium" is meant to include Mg alloys where Mg comprises the majority portion of the alloy. The most commonly known alloys are believed to be those of 60 magnesium alloyed with aluminum or zinc.

In the practice of the present invention it is essential that the Mg particles, which are recovered as the final product and which are intended for use as an inoculant for ferrous melts, have a high degree of rotundity and retain a thin protective coating of the sludge materials. The protective coating helps avoid the problems and dangers of handling, shipping, and storing the 65 4 GB 2 029 457A 4 finely-divided Mg particles; without a protective coating the Mg particles are subject to rapid oxidation and, in some cases, may cause an explosion. The Mg particles recovered by the present invention are generally required to be substantially within the range of from 8 to 100 mesh, preferably from 10 to 65 mesh, in order to be readily acceptacle to industries which inject them into molten ferrous metals through a lance.

Quite often sludge material is taken in molten or semi-molten form from the Mg-producing or Mg-casting operations and allowed to cool (freeze) into relatively large pieces or flakes. It is usually necessary to break up such large pieces into sizes which are acceptable in the hammer mill; this may be done by the use of jaw crushers or other convenient means.

It has been found that the pieces of Mg-containing matrix may be passed through a hammer 10 mill to break up the friable matrix without causing an appreciable amount of flattening or breaking of the rotund Mg particles, yet the hammer mill leaves a coating of the matrix material on the Mg particles. The material may be passed through the hammer mill a plurality of times, or through a series of two or more hammer mills to assure substantially complete pulverization matrix agglomerates without completely removing the protective coating on the Mg beads. In 15 contradistinction, attempts to free the Mg particles from the matrix material by passing the material through roll-mills, crusher mills, or ball-mills containing large heavy rolls or bars generally results in smashing or flattening a sizeable portion of the rotund Mg particles. If the first pass through the impact mill is found to have been insufficient to have pulverized the friable matrix to the desired extent, it may be run through the mill again using smaller grade openings 20 through which the particles fall.

After treatment in the hammer mill, the material may be screened to remove particles greater than 8 mesh and, if desired, remove any particles of less than 100 mesh. In the present process, however, there usually are no particles greater than 8 mesh in size. It is generally desirable to shake the screens to get rid of excess powdery matrix material which may still be 25 clinging to the coated Mg-particles without actually being a part of the contiguous coating.

There are a number of commercially available screens, including vibrated screens, which are suitable for use in this invention.

In those instances where the salt-mixture comprising the matrix material is hygroscopic, it is necessary that a relatively dry (less than 35% relative humidity, preferably less than 20%) atmosphere be provided during the process. This is especially important in the screening and grinding steps because moisture-dampened particles tend to cling to surfaces which they contact and interfere with classification of the particles. Also, if the product is to be used for molten ferrous metal inoculations, it is important that the particles be substantially dry and free-flowing.

The mixture of molten salt/molten Mg (or Mg alloy) to which the boroncontaining dispersant 35 is added may be, e.g., a Mg cell bath composition, a Mg cell sludge composition, a Mg (or Mg alloy) casting slag, or a Mg-alloying slag. Also, the molten mixture may be prepared by adding Mg (or Mg alloy) to the desired salt (or mixture of salts) or by adding additional Mg (or Mg alloy) to an existing Mg cell bath composition, Mg cell sludge composition, Mg (or Mg alloy) casting slag, or Mg-alloying slag. Adding additional Mg (or Mg alloy) to such already existing 40 mixtures is very beneficial in that it improves the economics of recovering saltm-coated metal particles or beads from such existing mixtures. It is also within the purview of the present invention to add Mg metal to a salt (or salt mixture) which initially contains little or no Mg metal. Furthermore, the Mg metal which may be added to any of the above described salts may contain various other ingredients or impurities, such as salt, dirt, oxides, other metals, mill scale, 45 or machining chemicals. Thus, "waste" pieces of Mg or scrap Mg may be incorporated into a useful product. Sometimes the sludges or slags from a Mg-production process or from a Mgcasting or Mg alloy-casting process will already contain very small amounts of boron, generally less than 25 ppm (as boron based on Mg content); it would be unusual for such mixtures to contain as much as 50 ppm or more.

A molten mixture of salt (matrix) and Mg or Mg alloy is provided and a boron-containing dispersing agent is added, with stirring, to distribute the dispersing agent throughout the melt and to cause the Mg or Mg alloy to disperse as small droplets in the melt. Following this the molten mixture is removed from the melting pot and allowed to cool (freeze) to a temperature which permits easy handling and to obtain the mixture as a friable matrix containing solid Mg or 55 Mg alloy rotund particles dispersed therein. The cooled, mixture is then broken up (if needed) into pieces suitable for feeding to a hammer mill where the friable matrix is broken away from the metal beads. The metal beads still retain a thin protective coating of the matrix adhered thereto. The matrix-coated (also called salt-coated) metal beads are separated from the pulverized matrix material by screening, by air-classifying, by tabling on a slanted table, or by any other 60 convenient separating means.

The amount of Mg or Mg alloy dispersed in the matrix should be limited to a concentration, by weight, of less than 42%; above this amount it is difficult to avoid having clusters of metal beads adhered to, or coalesced with, each other when cooled. Preferably, the amount of Mg or Mg alloy in the matrix is held to a maximum of 38 to 40% to be substantially assured of no 65 X GB 2 029 457A 5 "off-spec" metal, i.e., metal which is not present as small, rotund, discrete beads. There is no particular minimum amount of Mg or Mg alloy from an operability standpoint, but from a practical standpoint, it appears best if the amount of Mg or Mg alloy dispersed in the matrix is at least an amount such as is found in various sludges or slags from Mg- production or from casting operations. However, such low concentrations are beneficially increased by adding Mg or Mg alloy to the melts to bring the metal content up to 42%, preferably from 38 to 40%.

Any temperature at which the metal and the matrix is molten may be used and for most of the mixtures which may be used in the present invention, a temperature in the range of 670C to 820'C is usually employed. It has been found, in the case or Mg or Mg-Al in production sludges or casting slags, that the preferred temperature of the melt, during the dispersing step, 10 is from 730' to 790C. At less than 730C, the dispersing step generally requires more time and there appears to be a greater tendency for the small metal beads to re-coalesce into larger beads or into clusters. At temperatures of greater than 790C, there is a greater tendency for the molten Mg to burn at the surface of the melt and greater care must be exercised to blanket the melt with a substantially inert atmosphere during the melt operation and sometimes during 15 the pouring operation when the melt is removed from the melting vessel. Such "burning" oxidizes some of the Mg or MgO.

The amount of boron-containing dispersing agent should be a minimum (as boron) of 400 pprn (based on Mg or Mg alloy) and preferably from 800 to 2000 ppm. Greater amounts may be used but there is no additional benefit to be derived from such greater amounts.

The boron-containing dispersing agent may be any boron-containing mixture or compound which will dissolve in or release boron values into the matrix matrix, such as boric acid, alkali metal borates, borax, boron halides, boron oxides or metal perborates. Less preferred, because of expense or hazard, are the organo-boron compounds, such as boron hydrides or gaseous boron.

The use of very fine particle carbon, such as lampblack, may be beneficially added with the boron as a dispersing aid. Lampblack is known to be somewhat effective as a dispersing aid and, in fact, such fine particle carbon is sometimes found as a carbon residue of organic material which has found its way into sludge, flux, or slag material. The presence of such carbon residue in cell bath sludge, for instance, is known or believed to make coalescence of the 30 Mg difficult, thereby creating a need for additional coalescence agents (such as CaF,) when primary Mg is produced in fused salt electrolysis. The amount of lampblack, if it is added, may be up to about the amount of boron which is added, but preferably is only about half or less of the amount of boron added. If there is already an appreciable amount of very fine carbon in the slag or sludge, or in the Mg or Mg alloy added thereto, there may be little or no benefit to 35 adding more carbon.

The minimum amount of time involved in stirring the melt to disperse the added boron and the metal is somewhat dependent on the stirring speed, the temperature of the melt, the concentration of the Mg or Mg alloy, the viscosity of the melt, and the amount of boron added.

Lower temperatures, high Mg or Mg alloy concentrations, higher viscosities, and lower concentrations of boron generally require greater stirring times and/or stirring speeds. Gener ally, the amount of time involved ranges from 30 minutes under the slowest conditions to 0.5 minutes under the fastest conditions, assuming of course that the- stirrer is adequately sized for the volume of melt involved and is operated at an adequate speed. A four- blade stirrer, operated at a tip speed of from 1500 to 4000 feet/minute has been found to be particularly effective in 45 obtaining good mixing and good dispersions. Stirrers having from two to eight blades are ordinarily used. An air-motor provides a convenient and relatively safe means for powering the stirrer, though other power sources may be used.

The amount of boron found in the salt-coated metal beads after separation of the beads from the pulverized matrix is usually not more than from 100 to 200 ppm (on 100% Mg basis). This 50 small amount of boron is not a detrimental amount when the beads are employed as an inoculant material for molten ferrous metals.

The amount of matrix material (salt) adhered as a coating to the metal beads is normally in the range of from 2% to 20% of the total weight, and is preferably in the range of from 8% to 12% if the material is to be used as an inoculant for molten ferrous metals.

During the hammer-milling, screening, size-classification, or other handling of the salt-coated metal beads, it is preferred that the atmosphere in contact with the beads be dry or relatively dry. Many salts are hygroscopic and tend to pick up moisture from the air; this makes screening and classification difficult as the moisture tends to cause clinging of the particles to each other and to other surfaces. A relative humidity of less than 35%, preferably less than 20%, should 60 be used so as to avoid complications.

The pulverized matrix is beneficially recycled by adding more Mg or Mg alloy, and make-up salts if desired, and re-melting it for furtherformation and recovery of rotund metal beads. Such recycled salt will normally carry with it some of the boron values from the previous operation, thereby requiring very little, if any, additional boron to obtain the desired dispersion of melt.

6 GB2029457A 6 Also, any -off-spec- material from a given granule-forming operation may be recycled to become a part of a subsequent operation.

EXAMPLES

A series of samples were made under comparative conditions in a small demonstration plant using 20-lb (-9.07 kg) melts containing about 40% Mg metal in a pot about 7 inches (18 cm.) in diameter and about 10 inches (25.4 cm.) deep. The melts were done at about 1400'F + / - 25 (760C + / 14), stirring was done at about 4000-4500 rpm using a threebladed impeller of one-inch (2.54 cm.) blades which gave a tip speed of about 2094-2356 ft./min. (638-820 meters/min.), using a stirring time of about 60 seconds.

The melts were chilled to well below their freezing points by being poured onto a revolving chilled roller on a flaking machine where the frozen friable material formed as a thin sheet which broke up into flakes as it was scraped from the chilled roll by a scraper blade. The water- cooled roll has a diameter of 12 inches (30.48 cm.) and was 36 inches (91. 44 cm.) long.

Ineachbatchof material, representative sa m pies of the flakes (when it was apparent that some 15 dispersion had taken place) were photomicrographed at 4-power magnification and particle size distribution was measured using a ruler. From a visual study of the melts, the cooling, and/or the photomicrographs, the results were classified in one of the following categories:

1. No dispersion-this means that virtually all the Mg metal was present as one or more large pieces and there was no visible evidence that any of the Mg was present as small, discrete 20 globules or beads; 2. Totally coalesced-this means that some dispersion was apparent during stirring, but when stirring was stopped and before freezing occured on the chill-roll, it could be seen that the Mg globules had coalesced to form large particles or clusters of particles and rapidly lost their dispersity; 3. Partially coalesced-this means that when stirring was stopped, and before freezing occurred, a significant amount of the disperse Mg metal coalesced into large particles or clusters, yet an appreciable amount remained dispersed as small, rotund discrete beads; 4. Well dispersed-this means that after stirring there was no apparent coalescence of the small, rotund discrete Mg metal beads and virtually all the beads could pass through a 1 O-mesh 30 screen after being freed from entrapment in the friable matrix. This category is given in the examples as a mesh size, representing the number average size of the salt- covered Mg beads.

As used in these examples, the expression "small, discrete beads" refers to beads which are small enough to pass through a 1 O-mesh screen and which are not attached to other beads. The boron values are supplied as boric acid. The tests were made in a dry ambient atmosphere of 35 not more than 35% relative humidity so as to avoid moisture problems with those salts which are hygroscopic. Salt mixtures of the following compositions were tested.

Approx. % Compound in Salt Mixture 40 Sample No. MgC], NaCI KCL CaC12 CaF2 BaC12 p A 6.0 59.0 20.1 13.8 1.1 - B 12.0 55.3 18.8 12.9 1.1 - 45 c 18.0 51.5 17.5 12.0 1.0 - D 20.0 50.0 17.0 11.5 1.0 - E 25.0 47.1 16.0 11.0 0.9 F 30.0 44.1 14.9 10.2 0.8 - G 36.0 40.2 13.6 9.5 0.7 - 50 H 18.2 52.0 17.7 12.1 0 - 1 17.8 51 17.3 11.9 2.0 - j 17.2 49.5 16.7 11.6 5.0 - K 17.9 51.3 17.4 11.9 1.0 0.5 L 17.0 49.0 16.5 11.5 0.9 5.0 55 m 16.2 46.7 15.8 10.6 0.7 10.0 N - 62.8 21.3 14.6 1.2 0 13.9 62.5 13.5 9.3 0.8 - p 10 73.0 9.7 6.7 0.6 - 60 The above salt samples were melted, the Mg metal content brought to about 40% and various amounts of boron or other ingredients were added with stirring. The visual observation of the amount of coalescence and dispersion was noted for each melt. The cooled flakes from the chilled roll were broken up in a hammer mill in those instances where the Mg metal was 65 1 1 55 7 GB2029457A 7 found to be---welldispersed---. Following the hammer milling the pulverant was screened to separate pulverized matrix from the salt-coated rotund Mg beads.

The following table demonstrates the amount of boron in the melts and the amount of coalescence or dispersion obtained. In the table,---DO-means ditto-.

No. Av.

Sample Boron Carbon Coalescence or Particle Variable Number ppm ppm Dispersion Size (mesh) Studied A 0 - well dispersed 50 boron A 500 - DO 50 DO A 1000 - DO 48 DO A 1500 - DO 45 DO A 2000 - DO 43 DO 15 c 0 Partially coalesced - - boron c 400 - well dispersed 20 DO c 1000 - DO 20 DO C 2000 - DO 20 DO 20 G 0 - no dispersion - boron G 400 - well dispersed 15 DO G 1000 - DO 15 DO G 2000 - DO 15 DO 25 H - - well dispersed 40 CaF2 1 - - totally coalescenced - DO j - - no dispersion - DO K - - well dispersed 35 BaC12 30 L - - DO 45 DO m - - DO 48 DO B 1950 - well dispersed 35 M9C12 D 1950 - DO 22 DO 35 G 1950 - DO 15 DO N - - well dispersed 55 M9C12 A DO 50 DO B - - DO 35 DO 40 c - - partially coalesced - DO E - - totally coalesced - DO F - - no dispersion - M9C12 G - - well dispersed 20 DO 45 c - - partially coalesced - NaC] 0 - - well dispersed 25 DO p - - well dispersed 35 DO 50 c 0 partially coalesced - lampblack c 400 well dispersed 35 DO c 1700 DO 35 DO c 3200 DO 35 DO Hammer milling of the flakes in a single stage with the pulverant failing through a 3/8-inch gate generally results in salt-coated beads having a Mg content of from 65 to 70% by weight. Passing the pulverant through a second hammer mill stage having a 3/8-inch or 3/1 6-inch grate results in salt-coated Mg beads having a Mg content of from 75 to 80% by weight. Subsequent hammer mill stages having a 10-mesh grate generally results in salt-coated beads having a Mg content of from 80 to 95% by weight. The repeated hammer miling does not appear to substantially affect the size or rotundity of the Mg bead, but merely reduces the thickness of the salt-coating on the beads. If desired, additional -polishing- of the Mg beads to further reduce the thickness of the salt-coating may be performed.

8 GB 2 029 457A 8 A collection of batches having bead sizes of less than 10 mesh is screened and is found to have a nominal particle size distribution as follows:

Particle Size Range 5 (U.S. Standard Sieve) Percent of Total X 20 27.6 X 30 20.7 30 X 40 27.4 10 X 50 24.3 As can be seen from the foregoing experiments, the tendency of the molten Mg or Mg alloy to become dispersed in the molten salt is somewhat dependent on the salt composition. 15 Increasing the MgCl2 or CaF2 content generally causes a greater tendency to coalesce.

Increasing the BaCl2 content has little effect, but the tendency is toward better dispersion.

Increasing the NaCl content generally increases the tendency to disperse, but this may be partly due to the accompanying reduction in MgCl2.

In any event the present process provides a means for employing salt mixtures from various 20 sources whereby, with the addition of boron values, a well dispersed Mg metal is substantially assured without having to adjust the process to accommodate the various tendencies toward coalescence which may be found with the various sources. Thus salt mixtures from various sources, e.g., Mg cell feed, Mg cell sludge, Mg or Mg alloy slags, etc., may be used in the present process with the Mg or Mg alloy content being adjusted upwardly, if desired, and by 25 employing a boron dispersant the Mg or Mg alloy may be consistently dispersed in the melt to achieve substantially regular sizes of rotund beads without having to adjust the process to accommodate the variances in the salt mixtures.

Though the present disclosure is made with particular emphasis on the use of salt-coated Mg beads as inoculants for molten ferrous metals, it will be readily understood by practitioners of the relevant arts that the beads have other uses such as for additives to other molten metals.

Embodiments other than those illustrated in this disclosure will become apparent to practitioners of the relevant arts, upon learning of this invention, and the present invention is limited only by the following claims and not by the particular embodiments illustrated here.

Claims (20)

1. A process which comprises adding a boron-containing dispersing agent to a molten mixture of salt and Mg or Mg alloy, stirring the mixture to obtain thorough mixing of the boron-containing dispersing agent and the molten Mg or Mg alloy in the molten salt, and cooling the mixture, thereby obtaining a frozen, friable, salt matrix having dispersed therein solid rotund particles of Mg or Mg alloy.

2. The process of Claim 1 wherein the amount of Mg or Mg alloy in the salt is up to 42% by weight.

3. The process of Claim 2 wherein the amount of Mg or Mg alloy in the salt is in the range 45 of from 38% to 40% by weight.

4. The process of Claim 1, 2 or 3 wherein the temperature of the molten mixture is in the range of from 670C to 82WC.

5. The process of Claim 4 wherein the temperature of the molten mixture is in the range of from 73WC to 79WC.

6. The process of any one of the preceding claims wherein the stirring is performed for a period of time in the range of from 0.5 minute to 30 minutes, and wherein the stirring is performed using a stirrer having a tip speed in the range of from 450 to 1220 meters/minute.

7. The process of any one of the preceding claims wherein the boroncontaining dispersing agent is selected from boric acid, alkali metal borates, borax, boron halides, boron oxides, metal 55 perborates, organo-boron compounds, boron hydrides and gaseous boron, and wherein the amount of boron-containing dispersing agent, as boron, is at least 400 ppm based on Mg or Mg alloy.

8. The process of any one of the preceding claims wherein the salt-coated Mg or Mg alloy particles comprise from 2% to 20% by weight of salt.

9. The process of Claim 8 wherein the salt-coated Mg or Mg alloy particles comprise from 8% to 12% by weight of salt.

10. The process of any one of the preceding claims including the steps of pulverizing the frozen salt mixture in a hammer mill to recover rotund, salt-coated Mg or Mg alloy particles from entrapment therein and 1 k 1 9 GB2029457A 9 separating the Mg or Mg alloy particles from the pulverized salt matrix.

11. The process of Claim 10 wherein the pulverizing is performed by a plurality of passes through a hammer mill to obtain substantially all the pulverant through 8 mesh openings, wherein the material, after pulverizing in a hammer mill, is screened to collect salt-coated Mg or Mg alloy particles in the range of from 10 to 65 mesh, and wherein the amount of boroncontaining dispersing agent, as boron, is in the range of from 800 to 2000 ppm based on Mg or Mg alloy.

12. The process of any one of the preceding claims wherein the molten mixture contains very fine carbon in an amount up to the amount of boron.

13. A process for producing rotund, salt-coated granules of Mg or Mg alloy containing from 10 2% to 20% by weight of salt as a coating, and having a particle size in the range of from 10 to 65 mesh, said granules being useful as an inoculant material for molten ferrous metal, said process comprising melting together, at a temperature in the range of from 670'C to 820'C, a mixture comprising 1 up to 42% by weight of Mg or Mg alloy, at least 58% by weight of salt selected from alkali metal halide and alkaline earth metal halide, and at least 400 ppm, as boron, of a boron-containin.g dispersing agent based on Mg or Mg alloy, stirring the melt for a time sufficient to substantially disperse the boron-containing dispersing 20 agent and the Mg or Mg alloy in the salt, cooling the melt to freeze the salt and the Mg or Mg alloy dispersed therein, pulverizing the frozen salt matrix in a hammer mill to free the Mg or Mg alloy particles entrapped therein, and said particles still retaining a salt coating adhered thereto, and separating from the pulverant the salt-coated Mg or Mg alloy particles in the range of 25 from 10 to 6 5 mesh.

14. A process as claimed in claim 1 substantially as hereinbefore in any one of the Examples.

15. A frozen, friable, salt matrix having dispersed therein solid rotund particles of Mg or Mg alloy and which has been produced by a process as claimed in any one of claims 1 to 9 and 14. 30

16. Mg or Mg alloy particles which have been recovered by a process as claimed in any one of claims 10 to 14.

17. A metallurgical process involving the use of Mg or Mg alloy particles as claimed in claim 16.

18. The desulfurization of steel involving the use of Mg or Mg alloy particles as claimed in 35 claim 16.

19. The preparation of ductile iron involving the use of Mg or Mg alloy particles as claimed in claim 16.

20. A product of a process as claimed in any one of claims 17 to 19, and any product derived therefrom.

Printed for Her Majesty's Stationery Office by Burgess Et Son (Abingdon) Ltd.-1 980. Published at The Patent Office, 2 5 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.

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